CN107857773B - The quinazolinone boride that 2- nitrogen heteroaromatic rings replace - Google Patents

The quinazolinone boride that 2- nitrogen heteroaromatic rings replace Download PDF

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CN107857773B
CN107857773B CN201710088903.3A CN201710088903A CN107857773B CN 107857773 B CN107857773 B CN 107857773B CN 201710088903 A CN201710088903 A CN 201710088903A CN 107857773 B CN107857773 B CN 107857773B
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quinazolinone
hydrogen quinazoline
boride
reaction
heteroaromatic rings
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CN107857773A (en
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宋智彬
傅杨
周佳
白雪娇
潘颖
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Jiangxi Normal University
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Abstract

The present invention relates to a kind of novel efficient organic fluorescence molecules --- and the quinazolinone boride that 2- nitrogen heteroaromatic rings replace, the quinazolinone boride which replaces can be Material synthesis by the quianzolinones and boron-containing compound that 2- nitrogen heteroaromatic rings replace.Since the quinazolinone parent that 2- nitrogen heteroaromatic rings replace can introduce other groups, by being reacted from different borides, novel material of fluoran fuctional pigments can be synthesized, such as introduce conjugation aromatic rings or aromatic heterocycle, conjugated system can be made to increase, or introduce electron donating group such as triphenylamine, diethylamine etc., keep the launch wavelength of these compounds mobile to long wave direction, and then obtain novel, the fluorescent molecule with various launch wavelengths.Fluorescent material prepared by this molecule will be widely used in the fields such as luminous and display device, chemical industry, biological medicine, pesticide, military project, intelligent terminal.

Description

The quinazolinone boride that 2- nitrogen heteroaromatic rings replace
Technical field
The present invention relates to Functional dye fields, and in particular to a kind of novel luminescent organic molecule --- 2- nitrogen heteroaromatic rings take The quinazolinone boride in generation.
Background technique
The multiple color and excellent luminescent properties and unique processing that functional organic pigment molecule can be presented with it Performance, can convenient adjusting molecular structure, for a long time by the favor of researcher, and light emitting diode, solar battery, field imitate Answer transistor, multifunctional intellectual display terminal, biomedical imaging, photodynamic therapy, communication and signal transduction, environment inspection The fields such as survey, sensor are widely used, and are one of the research hotspots of functional form organic molecule in recent years.
Boron has unique steric configuration and electronic structure, former by introducing boron in functional form organic pigment molecular structure Son can effectively adjust its Photophysics, while boracic organic compound also has special chemical stability.Especially four The organic B complex of corrdination type, luminescent properties are superior, since its high molar absorption coefficient, good photostability and chemistry are steady It is qualitative, it is got in terms of Organic Light Emitting Diode OLED and metal ion sensing, cell imaging, photodynamic therapy Carry out more applications.But synthesis step is more, and purifying is complex, especially classical BODIPY type boracic complex dye point Son.
By two nitrogen ligands of Quinazolinone-containing structural unit, (or it is corresponding derivative by simple synthesis step by the present invention Object) it is coordinated with boron, the quinazolinone boride that a kind of novel 2- nitrogen heteroaromatic rings replace is obtained, is a kind of novel organic hair Luminescent material.In this way, can effective conjugated system in further expansion quinazolinone molecular structure, realize and improve material Luminous efficiency itself adjusts launch wavelength, or even changes illumination mode, extends the purpose of luminescent lifetime.Due to the boron after coordination Complex space structure is X-type, can inhibit the accumulation between molecule-molecule, and be expected to obtain has preferably under solution and solid-state The luminescent material of luminescent properties.There is potential application value in terms of display device, electronic material, biological medicine.
Summary of the invention
The purpose of the present invention is to provide a kind of novel luminescent organic molecules --- the quinazolinone that 2- nitrogen heteroaromatic rings replace Boride and preparation method thereof.
The quinazolinone boride that a kind of 2- nitrogen heteroaromatic rings replace has the general structure such as following formula I or formula II:
Wherein, nitrogen heteroaromatic rings (A ring) can be with are as follows: pyrroles, pyridine, quinoline, indoles, thiazole, oxazole, imidazoles, benzothiazole, Benzoxazoles, benzimidazole, pyridazine, pyrazine, pyrimidine, quinoxaline, purine etc..
Functional group X can be halogen atom, alkynyl, phenyl, substituted-phenyl, hydroxyl, alkyl, alkoxy, phenol oxygroup, substitution Phenol oxygroup, adjacent diphenol oxygroup, replaces the groups such as adjacent diphenol oxygroup, salicylate, substituted salicylic acid root at cyano.
R1~R2 can for alkyl, halogen atom, alkenyl, alkynyl, phenyl, substituted-phenyl, aryl, substituted aryl, hydroxyl, Alkoxy, phenol oxygroup, acyl group, aldehyde radical, carboxyl, amide groups, nitro, amino, substituted-amino, heterocycle, substituted heterocyclic radical, cyanogen The groups such as base, sulfonic group, sulfydryl, alkylthio group.
The quinazolinone boride that above-mentioned 2- nitrogen heteroaromatic rings replace can by Quinazolinone-containing structural unit two nitrogen ligands (or Its corresponding derivative) with boron compound be Material synthesis.
The preparation method for the quinazolinone boride that above-mentioned 2- nitrogen heteroaromatic rings replace:
In the round-bottomed flask being protected from light, two nitrogen ligands that a certain amount of Quinazolinone-containing structural unit is added (or accordingly spread out Biology), in nonpolar solvent, corresponding boride is added according to specific reaction therebetween in back flow reaction several hours.Use high pressure Liquid chromatogram (HPLC) and thin-layer chromatography (TLC) track entire reaction process, judge reaction end.After reaction terminating, reaction solution After the processing such as washed, extraction, obtained extract liquor is concentrated with Rotary Evaporators, removes the mixture obtained after solvent, is utilized Column chromatography chromatogram separation, obtains target product.
Obtained target product is dissolved in deuterated reagent DMSO-d6 or CDCl3In, it can pass through1H NMR,13C NMR, The methods of HRMS confirms product structure.
The fluorescence property measurement for the quinazolinone boride that this kind of 2- nitrogen heteroaromatic rings replace, mainly comprises the steps that
(1) product is dissolved in acetonitrile solvent, is configured to a certain concentration, determine compound most using Fluorescence Spectrometer Big excitation wavelength and maximum emission wavelength, according to maximum excitation wavelength and the maximum emission wavelength numerical measuring product in solution shape Fluorescence quantum yield under state.
(2) solid powder of compound products is directly placed into Fluorescence Spectrometer, determines compound products solid-state like Maximum excitation wavelength and maximum emission wavelength under state, according to maximum excitation wavelength and the maximum emission wavelength numerical measuring product Fluorescence quantum yield under solid states.
The quinazolinone boride that this kind of 2- nitrogen heteroaromatic rings replace can be used to prepare highly efficient fluorescent material, preparation it is efficient Fluorescent material has many advantages, such as that property is stable, save the convenient, visibility of material and brightness is high.
Beneficial effects of the present invention: the quinazolinone boride and other existing boron that 2- nitrogen heteroaromatic rings of the invention replace Compound, which is compared, has fluorescence quantum efficiency height, all has the preferable characteristics of luminescence, synthesis under solution and solid-state two states It is easy, yield is higher, can be the gram-grade even feather weight large-scale production the advantages that；It is introduced by group, the launch wavelength of compound Can be mobile to long wave direction, and then obtain novel, the fluorescent molecule with various launch wavelengths, these molecules can be used for preparing Highly efficient fluorescent material；Preparation method of the invention is simple, raw material is easy to get, yield is higher, and therefore, this novel compound can answer It for fields such as luminous and display device, chemical industry, biological medicine, pesticide, military project, intelligent terminals, and is China in functional material A kind of novel fluorescent material is developed in field.
Detailed description of the invention
Fig. 1 is quinazolinone boron compound prepared by example 11H NMR spectra.
Fig. 2 is quinazolinone boron compound prepared by example 113C NMR spectra.
Fig. 3 is the crystal structure figure of quinazolinone boron compound prepared by example 1.
Fig. 4 is uv absorption spectra of the quinazolinone boron compound in acetonitrile prepared by example 1.
Fig. 5 is fluorescence emission spectrogram of compound of the quinazolinone boron compound in acetonitrile prepared by example 1.
Fig. 6 is fluorescence emission spectrogram of compound of the quinazolinone boron compound under solid states prepared by example 1.
Fig. 7 is luminous photo of the quinazolinone boron compound under solution and solid states prepared by example 1.
Specific embodiment
Below with reference to specific example, the present invention is further elaborated, but patent right is not limited to these embodiments.
Embodiment 1:
In 100mL reactor, the bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one 3.50g (10mmol) is added, adds Entering 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second Ether compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloro is used in layering Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for aqueous solution, distillation water washing The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 88%.It is product below Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1H NMR(400MHz,CDCl3) δ=9.14-9.16 (m, 1H), 8.70-8.74 (m, 1H), 8.61-8.63 (m, 1H),8.29-8.30(m,1H),8.20-8.23(m,1H),8.03-8.06(m,1H),7.78-7.80(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=160.8,150.1,148.0,147.3,145.6,142.6,138.0, 130.6,130.3,129.1,125.0,122.5,121.3ppm.
HRMS m/z[M+H]+calcd:349.9906；found:349.9910.
Fluorescence quantum yield: 0.94 (solution), 0.30 (solid-state)
Following table is the associated light performance parameter of product prepared by embodiment 1:
Embodiment 2:
In 100mL reactor, 2- (2- quinolyl) -3- hydrogen quinazoline-4-one 3.21g (10mmol) is added, is added 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for aqueous solution, distillation water washing The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 85%.It is the core of product below Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1H NMR(400MHz,CDCl3) δ=8.35-8.33 (m, 1H), 8.08-8.06 (m, 1H), 7.88-7.80 (m, 2H),7.60-7.58(m,2H),7.52-7.53(m,1H),7.42-7.45(m,3H)ppm.
13C NMR (100MHz, CDCl3) δ=175.6,163.8,154.3,149.4,147.5,134.9,132.7, 131.6,129.8,129.0,128.0,127.4,126.8,126.3,122.5,121.8,118.6ppm.
HRMS m/z[M+H]+calcd:322.0958；found:322.0963.
Fluorescence quantum yield: 0.90 (solution), 0.50 (solid-state)
Embodiment 3:
In 100mL reactor, the bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one 4.00g (10mmol) is added, adds Entering 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second Ether compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloro is used in layering Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for aqueous solution, distillation water washing The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 85%.It is product below Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1H NMR(400MHz,CDCl3) δ=8.32-8.34 (m, 1H), 8.05-8.07 (m, 1H), 7.84-7.86 (m, 2H),7.61-7.63(m,2H),7.52-7.53(m,1H),7.42-7.45(m,2H)ppm.
13C NMR (100MHz, CDCl3) δ=175.1,163.0,154.0,149.1,147.5,134.5,132.2, 131.0,129.2,128.6,127.8,127.1,126.3,126.0,122.1,121.5,118.0ppm.
HRMS m/z[M+H]+calcd:400.0063；found:400.0058.
Fluorescence quantum yield: 0.82 (solution), 0.56 (solid-state)
Embodiment 4:
In 100mL reactor, 6- dimethylamino -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 3.64g is added (10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into three Boron fluoride ether complex is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, Layering, is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution distills water washing several times, organic phase rotary evaporation Instrument concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 85%.With Under be product nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1H NMR(400MHz,CDCl3) δ=8.12-8.14 (m, 1H), 8.01-8.03 (m, 1H), 7.74-7.76 (m, 2H),7.51-7.53(m,2H),7.32-7.33(m,1H),7.22-7.25(m,2H),3.35(s,6H)ppm.
13C NMR (100MHz, CDCl3) δ=170.1,160.0,151.0,145.1,142.5,130.5,130.2, 129.8,128.2,127.5,126.4,125.1,124.3,123.0,122.1,121.5,118.0,45.2ppm.
HRMS m/z[M+H]+calcd:365.1380；found:365.1386.
Fluorescence quantum yield: 0.89 (solution), 0.41 (solid-state)
Embodiment 5:
In 100mL reactor, 6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 4.21g is added (10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into three Boron fluoride ether complex is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, Layering, is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution distills water washing several times, organic phase rotary evaporation Instrument concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 85%.With Under be product nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1H NMR(400MHz,CDCl3) δ=8.22-8.24 (m, 1H), 8.05-8.07 (m, 1H), 7.78-7.80 (m, 2H),7.59-7.60(m,2H),7.49-7.51(m,2H),7.41-7.43(m,2H),7.35-7.37(m,2H),7.22-7.25 (m,2H),3.35(s,6H)ppm.
13C NMR (100MHz, CDCl3) δ=171.1,161.0,150.0,144.1,141.5,132.8,130.6, 129.2,128.8,127.9,127.2,126.5,125.9,125.4,124.8,124.0,123.5 122.8,121.7, 120.5,116.2,100.1,96.2ppm
HRMS m/z[M+H]+calcd:422.1271；found:422.1265.
Fluorescence quantum yield: 0.70 (solution), 0.65 (solid-state)
Embodiment 6:
In 100mL reactor, 6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 4.21g is added (10mmol), addition 50mL tetrahydrofuran be solvent, after being uniformly mixed, be added triethylamine 8.5mL (60mmol), then plus The tetrahydrofuran solution for entering triphenyl borine is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, It stands, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase rotates for aqueous solution, distillation water washing Evaporimeter concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield is 85%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below:
1H NMR(400MHz,CDCl3) δ=8.12-8.14 (m, 1H), 8.01-8.03 (m, 1H), 7.75-7.80 (m, 6H),7.56-7.57(m,2H),7.49-7.51(m,2H),7.41-7.47(m,6H),7.32-7.36(m,4H),7.21-7.23 (m,2H)ppm.
13C NMR (100MHz, CDCl3) δ=171.1,161.0,150.0,144.1,141.5,132.8,130.6, 129.2,128.8,128.5,128.2,128.0,127.8,127.4,126.8,126.0,125.5 124.8,123.7, 122.5,119.2ppm
HRMS m/z[M+H]+calcd:438.1772；found:438.1763.
Fluorescence quantum yield: 0.56 (solution), 0.42 (solid-state)
Embodiment 7:
In 100mL reactor, 2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 2.23g (10mmol) is added, is added 50mL toluene is solvent, after being uniformly mixed, is added catechol 1.1g (10mmol), triethylamine 8.5mL (60mmol) connects Addition boron trifluoride ether compound, be heated to reflux, reaction material liquid for 24 hours, is poured into water after reaction by reaction In, it stands, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase is used for aqueous solution, distillation water washing Rotary Evaporators concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield It is 89%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below:
1H NMR (400MHz, DMSO-d6) δ=8.32-8.33 (m, 1H), 8.09-8.10 (m, 1H), 7.77-7.78 (m, 1H),7.62-7.63(m,1H),7.41-7.21(m,1H),7.35-7.31(m,1H),7.06-7.02(m,1H),6.65(d,J =8Hz, 2H), 6.56 (d, J=8Hz, 2H) ppm.
13C NMR (100MHz, DMSO-d6) δ=171.9,162.41,154.6,149.7,145.6,140.9,137.8, 133.4,128.6,125.7,122.5 120.9,119.69,116.92,112.9,110.21ppm.
HRMS m/z[M+H]+calcd:342.1044；found:342.1052.
Fluorescence quantum yield: 0.64 (solution), 0.10 (solid-state)
Embodiment 8:
In 100mL reactor, 2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 2.23g (10mmol) is added, is added 50mL toluene is solvent, after being uniformly mixed, is added salicylic acid 1.40g (10mmol), triethylamine 8.5mL (60mmol) connects Addition boron trifluoride ether compound, be heated to reflux, reaction material liquid for 24 hours, is poured into water after reaction by reaction In, it stands, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase is used for aqueous solution, distillation water washing Rotary Evaporators concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield It is 90%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below:
1H NMR (400MHz, DMSO-d6) δ=8.22-8.25 (m, 1H), 8.15-8.18 (m, 1H), 7.96-7.97 (m, 1H),7.85-7.89(m,1H),7.76-7.78(m,1H),7.54-7.58(m,1H),7.44-7.48(m,2H),7.05-7.07 (m,1H),6.95-7.03(m,3H)ppm.
13C NMR (100MHz, DMSO-d6) δ=174.1,170.2,164.2,147.8,145.6,135.5,133.5, 131.5,129.6,127.8,126.8,125.3,122.6,121.3,120.5,117.4,115.7,115.3,108.9, 102.6ppm.
HRMS[M+H]+calcd:370.0994；found:370.0102.
Fluorescence quantum yield: 0.54 (solution), 0.12 (solid-state)
Embodiment 9:
In 100mL reactor, 2- (2- pyrrole radicals) -3- hydrogen quinazoline-4-one 2.11g (10mmol) is added, is added 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for aqueous solution, distillation water washing The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 75%.It is the core of product below Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1δ=8.12 (d, J=8Hz, 1H) H NMR (400MHz, DMSO-d6), 7.87-7.89 (m, 1H), 7.72 (d, J= 8Hz,1H),7.49-7.53(m,1H),7.45-7.41(m,1H),7.12-7.16(m,1H),6.32-6.30(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=172.3,156.9,144.9,136.9,136.4,135.7,134.7, 134.3,130.9,123.0,120.2,110.0ppm.
HRMS:m/z[M+H]+calcd:260.0801；found:260.0805.
Fluorescence quantum yield: 0.74 (solution), 0.25 (solid-state)
Embodiment 10:
In 100mL reactor, 2- (6- propyl -2- quinolyl) -3- hydrogen quinazoline-4-one 3.59g (10mmol) is added, Addition 50mL toluene is solvent, after being uniformly mixed, is added catechol 1.1g (10mmol), triethylamine 8.5mL (60mmol) is subsequently added into boron trifluoride ether compound, is heated to reflux, and reaction for 24 hours, after reaction will reaction Feed liquid is poured into water, and is stood, and layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution, distillation water washing number Time, organic phase is concentrated with Rotary Evaporators, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained mesh Mark product, yield 89%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below:
1δ=10.5 H NMR (400MHz, DMSO-d6) (br s, 2H), 8.42-8.43 (m, 1H), 8.05-8.06 (m, 1H),7.72-7.74(m,1H),7.65-7.66(m,1H),7.41-7.42(m,2H),7.30-7.31(m,2H),7.06-7.08 (m,1H),2.62-2.64(m,2H),1.65-1.67(m,2H),0.92-0.94(m,3H)ppm.
13C NMR (100MHz, DMSO-d6) δ=170.5,160.2,151.4,145.6,142.7,130.8,130.1, 129.5,128.6,127.1,126.5,125.3,124.7,123.3,122.5,121.1,118.4,28.3,19.6, 12.5ppm.
HRMS m/z[M+H]+calcd:360.1514；found:360.1519.
Fluorescence quantum yield: 0.24 (solution), 0.20 (solid-state)
Embodiment 11:
In 100mL reactor, 2- (2- indyl) -3- hydrogen quinazoline-4-one 2.61g (10mmol) is added, is added 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for aqueous solution, distillation water washing The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 70%.It is the core of product below Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1H NMR(400MHz,CDCl3) δ=8.5 (br s, 1H), 7.91-7.92 (m, 1H), 7.70-7.71 (m, 1H), 7.45-7.48(m,1H),7.33-7.35(m,2H),7.26-7.28(m,3H),7.11-7.13(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=175.2,163.98,147.68,146.9,136.2,133.85, 128.6,127.78,126.93,122.4,121.8,120.6,117.98,115.58,115.17,102.6ppm.
HRMS:[M+H]+calcd:310.0958；found:310.0967.
Fluorescence quantum yield: 0.84 (solution), 0.35 (solid-state)
Embodiment 12:
In 100mL reactor, 2- (2-[4-morpholinodithio base) -3- hydrogen quinazoline-4-one 2.79g (10mmol) is added, adds Entering 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second Ether compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloro is used in layering Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for aqueous solution, distillation water washing The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 95%.It is product below Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1H NMR(400MHz,CDCl3) δ=8.23-8.25 (m, 1H), 7.95-7.96 (m, 1H), 7.63-7.59 (m, 2H),7.48-7.45(m,3H),7.34-7.35(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=176.1,163.98,156.3,152.9,147.68,146.92, 133.8,130.5 127.7,126.9,122.6,122.1 117.9,115.5,115.1ppm.
HRMS(ESI):m/z[M+H]+calcd:328.0522；found:328.0525.
Fluorescence quantum yield: 0.90 (solution), 0.60 (solid-state)
Embodiment 13:
In 100mL reactor, 2- (2- quinazolyl) -3- hydrogen quinazoline-4-one 2.79g (10mmol) is added, is added 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for aqueous solution, distillation water washing The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 86%.It is the core of product below Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1δ=9.50 (s, 1H) H NMR (400MHz, DMSO-d6), 8.42-8.43 (m, 1H), 7.85-7.86 (m, 2H), 7.66-7.68(m,2H),7.62-7.58(m 1H),7.26-7.23(m,1H),6.76(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=178.1,165.5,163.7,156.2,150.0,147.7,133.9, 132.8,128.2,127.8,122.1,119.0,117.0,115.7,114.9,111.9ppm.
HRMS(ESI):m/z[M+H]+calcd:323.0910；found:323.0915.
Fluorescence quantum yield: 0.84 (solution), 0.43 (solid-state)
Embodiment 14:
In 100mL reactor, 2- (6- nitro -2- quinazolyl) -3- hydrogen quinazoline-4-one 3.67g is added (10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into three Boron fluoride ether complex is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, Layering, is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution distills water washing several times, organic phase rotary evaporation Instrument concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 86%.With Under be product nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1δ=9.50 (s, 1H) H NMR (400MHz, DMSO-d6), 8.72-8.73 (m, 2H), 8.21-8.23 (m, 1H), 7.76-7.78(m,2H),7.65-7.67(m 1H),7.36-7.35(m,1H),7.21-7.23(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=178.1,170.5,167.7,159.8,155.0,149.7,142.9, 138.8,135.2,133.8,129.5,128.1,126.0,125.3,124.4,120.8.ppm.
HRMS(ESI):m/z[M+H]+calcd:368.0761；found:368.0753.
Fluorescence quantum yield: 0.34 (solution), 0.12 (solid-state)
Embodiment 15:
In 100mL reactor, 6- methoxyl group -2- (6- cyano -2- quinazolyl) -3- hydrogen quinazoline-4-one is added 3.72g (10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), then Boric acid is added, is heated to reflux, reaction material liquid for 24 hours, is poured into water by reaction after reaction, is stood, and dichloro is used in layering Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for aqueous solution, distillation water washing The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 86%.It is product below Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield:
1δ=10.5 H NMR (400MHz, DMSO-d6) (br s, 2H), 8.36-8.38 (m, 1H), 8.10-8.11 (m, 1H),7.80-7.81(m,1H),7.62-7.63(m,1H),7.39-7.40(m,1H),7.30-7.31(m,2H),7.01-7.02 (m,1H),3.85(s,3H)ppm.
13C NMR (100MHz, DMSO-d6) δ=171.5,161.2,152.4,146.6,143.7,131.8,131.1, 129.8,128.6,128.1,127.5,126.3,125.7,124.3,123.5,122.1,119.4,118.5,56.2ppm
HRMS(ESI):m/z[M+H]+calcd:373.1103；found:373.1109.
Fluorescence quantum yield: 0.36 (solution), 0.30 (solid-state)

Claims (4)

  1. The quinazolinone boride that 1.2- nitrogen heteroaromatic rings replace has the structure as shown in any structure formula in following structural:
  2. 2. the preparation method for the quinazolinone boride that 2- nitrogen heteroaromatic rings according to claim 1 replace, including following step It is rapid:
    (1) two nitrogen ligands or corresponding derivative of a certain amount of Quinazolinone-containing structural unit are added, in nonpolar solvent, Between corresponding boride and catechol, bigcatkin willow acid starting material be added according to specific reaction, adjust reaction solution to alkalinity with triethylamine, Back flow reaction 24 hours；
    (2) reaction material liquid is poured into water, is stood, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution, steaming Distilled water is washed several times, and organic phase is concentrated with Rotary Evaporators, removes the mixture obtained after solvent, utilizes column chromatography chromatogram point From obtained sterling；
    Wherein, two nitrogen ligands of the Quinazolinone-containing structural unit or corresponding derivative are
    The bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one,
    2- (2- quinolyl) -3- hydrogen quinazoline-4-one,
    The bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one,
    6- dimethylamino -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,
    6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,
    6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,
    2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,
    2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,
    2- (2- pyrrole radicals) -3- hydrogen quinazoline-4-one,
    2- (6- propyl -2- quinolyl) -3- hydrogen quinazoline-4-one,
    2- (2- indyl) -3- hydrogen quinazoline-4-one,
    2- (2-[4-morpholinodithio base) -3- hydrogen quinazoline-4-one,
    2- (2- quinazolyl) -3- hydrogen quinazoline-4-one,
    2- (6- nitro -2- quinazolyl) -3- hydrogen quinazoline-4-one, or
    6- methoxyl group -2- (6- cyano -2- quinazolyl) -3- hydrogen quinazoline-4-one.
  3. 3. preparation method according to claim 2, it is characterised in that: the boride is that boron trifluoride ether is compound Object, boric acid or triphenyl borine.
  4. 4. application of the quinazolinone boride that 2- nitrogen heteroaromatic rings according to claim 1 replace in fluorescent material.
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